Aromatic musks

ABSTRACT

The present invention relates to novel musk compounds, useful as fragrance materials which have the structure: ##STR1## wherein R is hydrogen or methyl and R 1  and R 2  are hydrogen, methyl, or ethyl, and provides methods for preparing these compounds from readily available intermediates. The invention also provides fragrance compositions which include the compounds, and processes for altering the organoleptic properties of perfume compositions, colognes and perfumed articles by adding organoleptically effective amounts of the compounds.

This is a continuation-in-part of application Ser. No. 394,847, filed July 2, 1982 now abandoned.

The present invention relates to novel aromatic musk compounds represented by the structure: ##STR2## wherein R is methyl or hydrogen and R₁ and R₂ are hydrogen, methyl, or ethyl, prepared according to the novel processes of this invention, and to the methods in which the compounds of this invention are used to alter, modify, enhance, or improve the organoleptic properties of fragrance compositions and of perfumed articles.

BACKGROUND OF THE INVENTION

Natural sources of musk and musk-like odor have been prized by perfumers for centuries. The limited availability of the natural materials has encouraged a search for inexpensive, more readily available synthetics with musk-like odor. The nitromusks were introduced in the late nineteenth century and much later synthetic musks which did not contain the nitro-function began to appear. Review articles by T. F. Wood in Givaudanian between 1968 and 1970 adumbrate the early search for synthetics with musk-like odor. Several of the synthetics mentioned in these articles have found large scale usage by the fragrance industry. However, the safety of certain nitromusks used in large quantities in fragrance compositions has been questioned. Consequently, there is a potential need for new synthetic musks which: may be used as replacements for the nitromusks, can be produced in an economic and straightforward manner, and are toxicologically safe. Such chemicals may be used in the duplication of fragrance notes, as well as in the creation of entirely new fragrance effects.

The review by T. F. Wood (see Givaudanian, September 1968, pp 6-7) discloses four tetralin derivatives which are presented in Table 1. These compounds are described as nonmusks, and are either odorless or nearly odorless. The organoleptic properties of the compounds of the present invention are completely different from those of the compounds disclosed in the Wood article, since unexpectedly they generally exhibit musk odor. Nowhere in the prior art is there any reference to the compounds of the present invention, or any mention of their organoleptic properties.

                  TABLE 1                                                          ______________________________________                                         Prior art compounds disclosed in Givaudanian, September                        1968, pp 6-7 and their odor descriptions are presented.                        STRUCTURE           ODOR DESCRIPTION                                           ______________________________________                                          ##STR3##           Nearly odorless. Devoid of musk odor.                       ##STR4##           Odorless. Nonmusk.                                          ##STR5##           Odorless. Nonmusk.                                          ##STR6##           Practically odorless.                                      ______________________________________                                    

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1. Illustrates the ¹ H-NMR spectrum of the inventive compound 3a.

FIG. 2. Illustrates the ¹³ C-NMR spectrum of the inventive compound 3a.

FIG. 3. Illustrates the Infrared spectrum of the inventive compound 3a.

FIG. 4. Illustrates the ¹ H-NMR spectrum of the inventive compound 4A.

FIG. 5. Illustrates the ¹³ C-NMR spectrum of the inventive compound 4a.

FIG. 6. Illustrates the Infrared spectrum of the inventive compound 4a.

FIG. 7. Illustrates the ¹ H-NMR spectrum of the inventive compound 3b.

FIG. 8. Illustrates the ¹³ C-NMR spectrum of the inventive compound 3b.

FIG. 9. Illustrates the Infrared spectrum of the inventive compound 3b.

FIG. 10. Illustrates the ¹ H-NMR spectrum of the inventive compound 3c.

FIG. 11. Illustrates the ¹³ C-NMR spectrum of the inventive compound 3c.

FIG. 12. Illustrates the Infrared spectrum of the inventive compound 3c.

FIG. 13. Illustrates the ¹ H-NMR spectrum of the inventive compound 3d.

FIG. 14. Illustrates the ¹³ C-NMR spectrum of the inventive compound 3d.

FIG. 15. Illustrates the Infrared spectrum of the inventive compound 3d.

THE INVENTION

It has been unexpectedly discovered that the compounds having the structure: ##STR7## wherein R is hydrogen or methyl and R₁ and R₂ are hydrogen, methyl or ethyl exhibit musk odor, often with a woody and sweet note.

Examples of some of the inventive compounds and their odor descriptions are presented in Table 2.

                  TABLE 2                                                          ______________________________________                                         INVENTIVE STRUCTURES                                                                             ODOR DESCRIPTION                                             ______________________________________                                          ##STR8##         Strong and excellent musk. Close in character to Musk                          Ambrette, but finer, sweeter, and more powerful.                               Exalting, with the character of the macrocyclic musks.        ##STR9##         Low-odored musk, woody and slightly sweet.                    ##STR10##        A sweet, exalting musk with a woody nuance.                   ##STR11##        Low-keyed musk, slightly sweet and woody.                     ##STR12##        Strong sweet musk with a rich woody nuance.                  ______________________________________                                    

The inventive compounds 3 and 4, where R is hydrogen or methyl and R₁ and R₂ are hydrogen, methyl or ethyl, may be prepared from a substituted tetrahydronaphthalene 1, wherein R₁ and R₂ are hydrogen, methyl or ethyl. The following reaction scheme illustrates two processes for conveniently and inexpensively preparing the compounds 3 and 4 of this invention from Compound 1.

The inventive compounds may be prepared by formylation, or formylation and methylation of the appropriate substituted tetrahydronaphthalene 1. The order of formylation and methylation is not critical, i.e. the substituted tetrahydronaphthalene 1 may first be formylated and then methylated, or vise-versa. ##STR13##

PROCESS I comprises: (a) methylation of Compound 1 to produce a substituted tetrahydronaphthalene 2, (b) formylation of Compound 2 to produce Compound 3, and (c) recovery of Compound 3.

PROCESS II comprises: (a) formylation of Compound 1 to produce a substituted tetrahydronaphthalene 4, (b) methylation of Compound 4 to produce Compound 3, and (c) recovery of Compound 3.

The Compound 4 is prepared by an abridged version of Process II which comprises: (a) formylation of Compound 1 to produce Compound 4; and (b) recovery of Compound 4.

The methylation reaction employed in either process may be accomplished in a variety of ways according to wellknown techniques. Such techniques are exemplified in R. B. Wagner and H. D. Zook "Synthetic Organic Chemistry", John Wiley, 1965, pp 226-252, and "The Chemistry of the Ether Linkage", Ed. S. Patai, Interscience, 1967, pp 445-498, which are incorporated herein by reference. Similarly, the formylation reaction may be accomplished in a variety of ways according to well-known techniques. Such techniques are exemplified in "Comprehensive Organic Chemistry", Pergamon, Ed. D. H. R. Barton and W. D. Ollis, 1979, Vol. 6, p 908, and "The Chemistry of the Carbonyl Group", Ed. S. Patai, Interscience, 1966, pp 233-302, which are incorporated herein by reference. Isolation and purification of the final products is achieved by conventional techniques including extraction, distillation, crystallization and the like.

On the basis of their valuable olfactory properties, the inventive compounds have been found to be suitable for use in fine fragrance compositions, as well as in perfumed products, such as soaps, detergents, deodorants, cosmetic preparations and the like. Such fragrance compositions may comprise an organoleptically effective amount of one or more of the novel compounds and at least one other organoleptic agent.

The term "organoleptically effective amount" is used herein to mean a level or amount of compound present in a perfume composition or perfumed article at which the incorporated compound(s) exhibit(s) a sensory effect.

Perfume compositions are carefully balanced, harmonious blends of essential oils, aroma chemicals, resinoids and other extracts of natural odorous materials. Each ingredient imparts its own characteristic effect to the composition. However, the overall sensory effect of the perfume composition will be at least the sum total of the effects of each of the ingredients. One or more of the novel tetrahydronaphthalene derivatives of this invention can be used to alter, modify or enhance the aroma characteristics of a perfume composition, for example, by utilizing or moderating the olfactory reaction contributed by another ingredient in the composition.

The terms "alter" and "modify" are used herein to mean supply or impart an aroma character or note to otherwise relatively odorless substances, or augment the existing fragrance characteristics of a composition which is deficient in some regard, or to supplement the existing fragrance or aroma impression to modify its quality, character or odor. The term "enhance" is used herein to mean the amplification or intensification of the quality thereof.

The amount of tetrahydronaphthalene derivative(s) of our invention which will be effective in perfume compositions as well as in perfumed articles and colognes depends on many factors. Such factors include the other ingredients in the composition or article, their concentrations, and the overall sensory effect desired. The tetrahydronaphthalene derivative(s) can be used in amounts of as little as 0.01% and often as low as 0.0001% to impart significant odor characteristics to perfumed articles, e.g. soaps, detergents, cosmetics, fabric softener compositions or articles, and other products. The amount employed can range up to about 80% of the fragrance components and up to about 7.0% of the quantity of perfumed article and will depend on considerations of cost, nature of the end product, the effect desired on the finished product, and the particular fragrance sought.

The tetrahydronaphthalene derivative(s) of our invention may be used alone or in combination with other ingredients in perfume compositions or as (an) olfactory component(s) in lacquers, brilliantines, pomades, shampoos, cosmetic preparations, powders and the like. When used as (an) olfactory component(s) as little as 0.0001% of tetrahydronaphthalene derivative(s), more preferably 1.0%, (based on weight of perfume composition) will suffice to impart a significant odor characteristic. Generally, no more than 7.0% of tetrahydronaphthalene derivative(s) based on the ultimate end-product is required in the perfume composition. Furthermore, the novel tetrahydronaphthalene derivative(s) may be employed in such a manner to provide a method for modifying, enhancing or improving the organoleptic properties of perfume compositions, colognes and perfumed articles by adding thereto an organoleptically effective amount of the novel chemicals of this invention.

The following examples are set forth herein to illustrate methods of synthesis of the compounds of this invention and their use in fragrance compositions. These examples are intended only to illustrate the embodiments of this invention and are in no way meant to limit the scope thereof.

EXAMPLE 1

This example provides a method for producing 1-hydroxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene. The method is illustrated by the following reaction sequence: ##STR14##

STEP A.

Concentrated hydrochloric acid (8,260 g, 86 mol) was added in one portion to 2,5-dimethyl-2,5-hexane diol (4,478 g, 46.65 mol). The resulting solution was heated for 6 h, with stirring at 22°-75° C., while passing hydrogen chloride gas (200 g). Then the reaction mixture was cooled to 25° C., hexane (3.5 L) added, and the mixture stirred vigorously. The organic layer was separated, washed with water (2×1 L), neutralized with 5% sodium bicarbonate solution and dried (Na₂ SO₄). The solvent was removed by distillation and the residue was crystallized from hexane to give 2,5-dimethyl-2,5-dichlorohexane (5,054 g), mp 67°-69° C.

STEP B.

2,5-Dimethyl-2,5-dichlorohexane (183 g, 1 mol) was stirred with m-cresol (129.6 g, 1.2 mol) and aluminum chloride (4 g) was added in one portion. The mixture was heated at 95° C., with stirring for 1.5 h, after which ethylene dichloride (100 mL) was added and then the heating was continued. After 1 h the mixture was cooled to 20° C. and poured onto an ice-water/hydrochloric acid mixture (150 mL, 10% HCl solution). The mixture was then extracted with toluene (500 mL). The organic layer was separated, washed with brine (3×50 mL) and dried (Na₂ SO₄). The solvent was removed by distillation and the residue was crystallized from a hexane/benzene solvent mixture to give 1-hydroxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (171 g), mp 133°-134° C., GLC purity 99%+. ¹ H-NMR (CDCl₃) δ6.82 (1H, broad s), 6.35 (1H, d, J= 1.4 Hz), 4.72 (1H, s), 2.30 (3H, s), 1.71 (4H, m), 1.49 (6H, s), 1.34 (6H, s). ¹³ C-NMR (CDCl₃) δ154.2 (1C, s), 147.8 (1C, s), 135.7 (1C, s), 128.0 (1C, s), 120.2 (1C, d), 114.6 (1C, d), 37.9 (1C, t), 35.2 (1C, t), 34.6 (1C, s), 33.7 (1C, s), 32.0 (2C, q), 28.5 (2C, q), 20.8 (1C, q). IR (KBr) 3,503 cm-, MS (m/e) 218 (M+, 24.7), 203 (100.0), 161 (55.1), 147 (23.9), 57 (10.9).

EXAMPLE 2

This example illustrates the preparation of 2-formyl-1-methoxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (3a) according to Process I. ##STR15##

(a) Methylation. A solution of sodium hydroxide (38 g, 0.95 mol) in water (1 L) was added to a mixture of 1-hydroxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (109 g, 0.5 mol), dimethyl sulfate (126 g, 1 mol) and Adogen 464* (21.6 g) in methylene dichloride (2 L). The reaction mixture was stirred vigorously at 25°-28° C. for 1 h, after which the organic layer was separated, combined with ammonium hydroxide solution (500 mL, 10%), and stirred vigorously at 20°-25° C. for 0.5 h. The organic layer was then separated and the washing procedure repeated, after which the organic layer was separated, washed with water (2×100 mL), then with brine (50 mL), and dried (Na₂ SO₄). The solvent was removed by distillation and the residue was crystallized from hexane yielding 1-methoxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (95 g), mp 49°-50° C., GLC purity 99 %+. ¹ H-NMR (CDCl₃) δ6.89 (1H, d, J=1.4 Hz), 6.63 (1H, d, J=1.4 Hz), 3.89 (3H, s), 2.41 (3H, s), 1.74 (4H, m), 1.48 (6H, s), 1.38 (6H, s). IR (KBr) 1273, 1257 cm⁻¹, MS (m/e) 232 (M+, 16.9), 217 (100.0), 175.3 (19.6), 218.6 (16.0).

(b) Formylation. 1-Methoxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (50 g, 0.2155 mol) was added to a stirred mixture of hexamethylenetetramine (31.4 g, 0.224 mol) and trifluoroacetic acid (250 mL) at 35°-40° C., under a nitrogen atmosphere. The stirred reaction mixture was heated to 85°-90° C. and maintained at this temperature for 1.5 h. Trifluoroacetic acid was removed by distillation and the residue was poured onto an ice-water mixture (800 mL). The mixture was then stirred for 0.5 h, neutralized with a 10% sodium carbonate solution, and the product extracted with benzene (2×150 mL). The combined extracts were washed with brine (50 mL) and dried (Na₂ SO₄). The solvent was then removed by distillation and the residue crystallized from hexane to provide 2-formyl-1-methoxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (14 g), mp 78° C., GLC purity 100%. ¹ H-NMR (CDCl₃) δ10.39 (1H, s), 6.93 (1H, s), 3.86 (3H, s), 2.49 (3H, s), 1.63 (4H, s), 1.39 (6H, s), 1.37 (6H, s), ¹³ C-NMR (CDCl₃) δ192.1 (1C, d), 165.4 (1C, s), 153.5 (1C, s), 138.3 (1C, s), 135.8 (1C, s), 125.8 (2C, s, d), 66.1 (1C, q) 38.1 (1C, t), 35.3 (1C, s), 34.8 (1C, t), 34.3 (1C, s), 31.7 (2C, q), 29.8 (2C, q), 20.8 (1C, q). IR (melt) 1245, 1682 cm⁻¹,MS (m/e) 260 M⁺, 20.8), 246 (18.7), 245 (100.0), 141 (12.3), 128 (13.2), 115 (13.0).

EXAMPLE 3

This example illustrates another formylation procedure that can be used in the preparation of 2-formyl-1-methoxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (3a) according to Process I.

1-Methoxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (23.2 g, 0.1 mol),prepared according to Example 2, was added to a stirred solution of acetic acid (18.2 g, 0.3 mol), 85% phosphoric acid (17.6 g, 0.15 mol), hydrochloric acid (28.7 g, 0.3 mol) and paraformaldehyde (7.3 g, 0.24 mol). The mixture was stirred and heated at 95° C. for 16 h. The reaction mixture was then cooled to 25° C., benzene (50 mL) added, and stirred vigorously. The organic layer was separated, washed with water (2×25 mL), neutralized with 5% sodium bicarbonate solution, and dried (Na₂ SO₄). The solvent was removed by distillation to provide 2-chloromethyl-1-methoxy-3,5,5,8,8,-pentamethyl-5,6,7,8-tetrahydronaphthalene, GLC purity 84%.

Sodium (2.87 g, 0.125 mol) was added in small pieces to methanol (40 mL) during 0.5 h at 25°-45° C., then nitropropane (13.35 g, 0.15 mol) was added. The mixture was heated with stirring at 65° C. during 0.25 h, then a slurry of 1-methoxy-2-chloromethyl-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (28 g, 0.1 mol) in methanol (50 mL) was added, in portions, during 0.25 h, at 65° C. The stirred mixture was heated at 65°-68° C. for 2.5 h, after which excess methanol was removed by distillation. The residue was dissolved in benzene (100 mL) and the solution washed with water (3×25 mL), then with brine (25 mL) and dried (Na₂ SO₄). The solvent was evaporated and the residue distilled to yield 18 g of material, (bp 116°-124° C./0.4 mm), which crystallized from hexane to provide 2-formyl-1-methoxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (3a), mp 78°-78.5° C. exhibiting the expected spectral data.

EXAMPLE 4

This example illustrates both the preparation of 2-formyl-1-hydroxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (4a) and 2-formyl-1-methoxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (3a) according to Process II. ##STR16##

(a) Formylation. Hexamethylenetetramine (21 g, 0.15 mol) and 1-hydroxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene were added in one portion with stirring to acetic acid (250 mL) and the mixture was heated at 95°-100° C. for 2 h. After cooling to 80°-85° C., water (250 mL) and concentrated hydrochloric acid (60 mL) were added and the mixture was heated at 95°-100° C. for a further 2 h. The reaction product was then cooled to 20° C., diethyl ether (150 mL) was added and the mixture was stirred vigorously. The organic layer was separated, washed with brine (2×50 mL), neutralized with 5% sodium bicarbonate solution (100 mL), and dried (Na₂ SO₄). The solvent was removed by distillation and the residue was distilled to yield 2-formyl-1-hydroxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (4a) (18 g), mp 91°-92° C., GLC purity 99%+. ¹ H-NMR (CDCl₃) δ12.92 (1H, s), 10.21 (1H, s), 6.73 (1H, s), 1.68 (3H, s), 1.67 (4H, s), 1.48 (6H, s), 1.32 (6H, s). ¹³ C-NMR (CDCl₃)67194.4 (1C, d), 163.5 (1C, s), 156.5 (1C, s), 138.0 (1C, s), 130.8 (1C, s), 120.1 (1C, d), 116.2 (1C, s), 37.7 (1C, t), 35.3 (1C, s), 34.6 (1C, t), 33.9 (1C, s), 31.0 (2C, q), 27.7 (2C, q), 17.8 (1C, q). IR (KBr) 1615, 1628 cm⁻¹, MS (m/e) 246.2 (M+, 23.9) 231.2 (100.0), 189.1 (19.9), 161.2 (19.2).

(b) Methylation. A solution of sodium hydroxide (0.98 g, 0.0244 mol) in water (24 mL) was added in one portion to a solution of 2-formyl-1-hydroxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (3 g, 0.0122 mol), dimethyl sulfate (3.07 g, 0.0244 mol) and Adogen 464* (0.56 g) in methylene dichloride (48 mL). The mixture was stirred vigorously at 38°-40° C. for 4 h. After cooling, the organic layer was separated, washed with brine (3×20 mL) and dried (Na₂ SO₄). The solvent was removed by distillation and the residue was distilled to yield 2-formyl-1-methoxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (3a), (2.5 g), mp 78° C. (from hexane), GLC purity 99.7%, exhibiting the expected spectral data.

EXAMPLE 5

This example illustrates the preparation of a starting material, 1-hydroxy-4,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene ##STR17## Employing procedures and materials similar to those described in Example 1, except that p-cresol was substituted for m-cresol, and the reaction was carried out in the presence of petroleum ether (bp 55°-100° C.) as solvent, there was obtained the desired product, 1-hydroxy-4,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene, 43% theor., GLC purity 98%, exhibiting the expected spectral data.

EXAMPLE 6

This example illustrates both the preparation of 2-formyl-1-hydroxy-4,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene and 2-formyl-1-methoxy-4,5,5,8,8,-pentamethyl-5,6,7,8-tetrahydronaphthalene (3b) according to Process II: ##STR18##

(a) Formylation. 1-Hydroxy-4,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (78 g, 0.358 mol) was stirred with glacial acetic acid (632 mL) and hexamethylenetetramine (93.6 g, 0.669 mol). The mixture was heated at 105°-110° C. for 10 h. Hot water (632 mL) was added and the heating was continued for an additional 2.5 h at 100° C. The mixture was cooled to 20° C., toluene (250 mL) was added, and the mixture was stirred vigorously. The organic layer was separated, washed with water (2×50 mL), then neutralized with 5% NaHCO₃ solution, and finally washed with brine (50 mL). The solvent was removed by distillation and the residue distilled to yield 2-formyl-1-hydroxy-4,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (45 g), bp 138°-146° C./1 mm, GLC purity 95%. ¹ H-NMR (CDCl₃) δ11.63 (1H, s), 9.73 (1H, s), 7.09 (1H, s), 2.52 (3H, s), 1.66 (3H, s), 1.47 (6H, s), 1.42 (6H, s). ¹³ C-NMR (CDCl₃) δ196 (1C, d), 159 (1C, s), 155 (1C, s), 134.7 (1C, d), 134.1 (1C, s), 128 (1C, s), 118.1 (1C, s), 39.3 (1C, t), 37.8 (1C, t), 36.5 (1C, s), 35.2 (1C, s), 28.7 (2C, q), 27.9 (2C, q), 23.5 (1C, q). IR (KBr) 1637 cm⁻ 1, MS (m/e) 246.2 (M⁺, 36.1), 231.2 (100.0), 161.2 (41.6), 189.1 (27.9).

(b) Methylation. 2-Formyl-1-hydroxy-4,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (42 g, 0.17 mol) was stirred with toluene (656 mL), and potassium hydroxide 85% (16.8 g, 0.255 mol) was added in one portion. The mixture was heated to 40° C., dimethyl sulfate (32.13 g, 0.255 mol) added at 40°-45° C. during 0.5 h, and the heating continued at 50° C. for an additional 1.5 h. The mixture was cooled to 20° C., neutralized with 5% HCl solution, then washed with water (20 mL), and finally washed with brine (25 mL). The solvent was removed by distillation and the residue distilled to give 2-formyl-1-methoxy-4,5,5,8,8- pentamethyl-5,6,7,8-tetrahydronaphthalene (36 g), bp 140°-142° C./1.5 mm, GLC purity 95%. Crystallization from hexane gave 28 g material, GLC purity 99%. ¹ H-NMR (CDCl₃) δ10.23 (2 H, s), 7.41 (1H, s), 3.89 (3H, s), 2.52 (3H, s), 1.63 (4H, s), 1.42 (6H, s), 1.40 (6H, s). ¹³ C-NMR (CDCl₃) δ189.9 (1C, d), 162.3 (1C, s), 153.1 (1C, s), 139.9 (1C, s), 132.7 (1C, s), 131.3 (1C, d), 126.5 (1C, s), 66.0 (1C, q), 39.4 (1C, t), 38.2 (1C, t), 36.4 (1C, s), 35.6 (1C, s), 30.0 (2C, q), 28.9 (2C, q), 23.7 (1C, q). IR (KBr) 1683, 1235 cm⁻¹, MS (m/e) 260.3 (M+, 46.3), 245.2 (100.0), 175 (38.5), 128 (31.1).

EXAMPLE 7

This example illustrates the preparation of a starting material, 3-ethyl-1-hydroxy-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene ##STR19## Employing procedures and materials similar to those described in Example 1, except that 3-ethylphenol was substituted for m-cresol, and the reaction was carried out in the presence of ethylene dichloride as solvent, there was obtained the desired product, 3-ethyl-1-hydroxy-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene 66% theor., GLC purity 99%+, exhibiting the expected spectral data.

EXAMPLE 8

This example illustrates both the preparation of 3-ethyl-2-formyl-1-hydroxy-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene and 3-ethyl-2-formyl-1-methoxy-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene (3c) according to Process II: ##STR20##

(a) Formylation. 3-Ethyl-1-hydroxy-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene (94 g, 0.405 mol) was stirred with glacial acetic acid (670 mL), and hexamethylenetetramine (102.6 g, 0.73 mol) was added in one portion. The mixture was heated at 95° C. for 3 h, hot water (670 mL) added, and the heating was continued for an additional 1.5 h at 100° C. The mixture was cooled to 20° C., toluene (200 mL) was added, and the mixture was stirred vigorously. The organic layer was separated, washed with water (3×150 mL), then neutralized with 5% NaHCO₃ solution, and finally washed with brine (50 mL). The solvent was evaporated and the residue distilled to give 3-ethyl-2-formyl-1-hydroxy-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene (77.9 g), bp 127°-132° C./0.5 mm, GLC purity 98%, ¹ H-NMR (CDCl₃) δ12.87 (1H, s), 10.20 (1 H, s), 6.72 (1H, s), 2.89 (2H, q), 1.65 (4H, m), 1.44 (6H, s), 1.30 (3H, t), 1.29 (6H, s). ¹³ C-NMR (CDCl₃) δ194.3 (1C, d), 163.6 (1C, s), 156.7 (1C, s), 144.6 (1C, s), 130.8 (1C, s), 118.5 (1C, d), 115.2 (1C, s), 37.7 (1C, t), 35.5 (1C, s), 34.7 (1C, t), 34.0 (1C, s), 31.1 (2C, q), 27.7 (2C, q), 24.8 (1C, t), 16.9 (1C, q). IR (KBr) 1609 cm⁻¹ MS (m/e) 260.3 (M+, 22.6), 245.2 (100.0), 203.3 (18.2), 246.2 (17.0).

(b) Methylation. 3-Ethyl-2-formyl-1-hydroxy-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene (48.2 g, 0.185 mol) was stirred with toluene (650 mL), and potassium hydroxide 85% (19.5 g, 0.296 mol) was added in one portion. The mixture was heated to 45° C. and dimethyl sulfate (35 g, 0.278 mol) was added during 0.5 h at 45°-50° C. The heating was continued for an additional 0.5 h at 50° C. The mixture was cooled to 20° C., neutralized with 5% hydrochloric acid, washed with water (50 mL), and then finally washed with brine (30 mL). Solvent was removed by distillation and the residue distilled to give 3ethyl-2-formyl-1-methoxy-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene (40.6 g), GLC purity 98%. Crystallization from hexane gave 27 g material, GLC purity 99%. ¹ H-NMR (CDCl₃) δ10.38 (1H, s), 6.97 (1H, s), 3.85 (3H, s), 2.89 (2H, q), 1.64 (4H, s), 1.40 (6H, s), 1.28 (6H, s), 1.20 (3H, t). ¹³ C-NMR (CDCl₃) δ192.0 (1C, d), 165.3 (1C, s), 153.6 (1C, s), 144.4 (1C, s), 135.7 (1C, s), 125.3 (1C, s), 124.1 (1C, d), 66.0 (1C, q), 38.1 (1C, t), 35.4 (1C, s), 34.8 (1C, t), 34.3 (1C, s), 31.8 (2C, q), 29.8 (2C, q), 26.6 (1C, t), 15.7 (1C, q). IR (KBr) 1275, 1263 cm⁻¹, MS (M/e) 274.2 (M+, 17.1), 258.1 (100.0), 260.3 (20.3), 128.1 (15.1).

EXAMPLE 9

This example illustrates the preparation of a starting material, 1-hydroxy-3,4,5,5,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalene ##STR21##

Employing procedures and materials similar to those described in Example 1, except that 3,4-dimethylphenol was substituted for m-cresol, and the reaction was carried out in the presence of ethylene dichloride as solvent, there was obtained 1-hydroxy-3,4,5,5,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalene, 15% theor., GLC purity 100%, exhibiting the expected spectral data.

EXAMPLE 10

This example illustrates the preparation of 2-formyl-1-hydroxy-3,4,5,5,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalene and 2-formyl-1-methoxy-3,4,5,5,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalene (3d) according to Process II: ##STR22##

(a) Formrylation. 1-Hydroxy-3,4,5,5,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalene (15 g, 0.0646 mol) was stirred with glacial acetic acid (100 mL), and hexamethylenetetramine (15 g, 0.107 mol) was added in one portion. The mixture was heated at 100° C. for 2 h. Hot water (100 mL) was added and the heating continued for an additional 0.5 h at 100° C. The mixture was cooled to 20° C., toluene (25 mL) was added, and the mixture was stirred vigorously. The organic layer was separated, washed with water (2×10 mL), then neutralized with 5% NaHCO₃ solution and finally washed with brine (10 mL). The solvent was removed by distillation, and the residue crystallized from hexane, to give 2-formyl-1-hydroxy-3,4,5,5,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalene (8.8 g), GLC purity 94%. ¹ H-NMR (CDCl₃) δ12.94 (1H, s), 10.36 (1H, s), 2.43 (3H, s), 2.36 (3H, s), 1.65 (4H, s), 1.48 (6H, s), 1.46 (6H, s). ¹³ C-NMR (CDCl₃) δ195.4 (1C, d), 161.4 (1C, s), 156.0 (1C, s), 138.0 (1C, s), 131.9 (1C, s), 126.6 (1C, s), 116.7 (1C, s), 40.2 (1C, t), 37.9 (1C, t), 36.5 (1C, s), 35.1 (1C, s), 29.5 (2C, q), 28.1 (2C, q), 19.3 (1C, q), 14.1 (1C, q). IR (KBr) 1628 cm⁻¹, MS (m/e) 260.3 (M+, 38.6), 245.2 (100.0), 175.1 (28.7), 189.1 (20.1).

(b) Methylation. 2-Formyl-1-hydroxy-3,4,5,5,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalene (8.7 g, 0.0335 mol) was stirred with toluene (60 mL), and potassium hydroxide 85% (3.1 g, 0.047 mol) was added in one portion. The mixture was heated to 55° C., dimethyl sulfate (6.3 g, 0.05 mol) added during 0.5 h at 55°-60° C., and the heating continued at 55°-60° C. for 4 h. The mixture was cooled to 20° C., neutralized with 5% hydrochloric acid, then washed with water (10 mL), and finally washed with brine (10 mL). The solvent was removed by distillation and the residue distilled to give 2-formyl-1-methoxy-3,4,5,5,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalene (5.8 g), GLC purity 97%. Crystallization from hexane gave 3.5 g material with GLC purity 100%. ¹ H-NMR (CDCl₃) δ10.40 (1H, s), 3.78 (3H, s), 2.40 (3H, s), 2.37 (3H, s), 1.64 (4H, s), 1.45 (6H, s), 1.42 (6H, s). ¹³ C-NMR (CDCl₃) δ193.5 (1C, d), 162.9 (1C, s), 151.6 (1C, s), 137.7 (1C, s), 136.7 (1C, s), 132.5 (1C, s), 126.9 (1C, s), 65.7 (1C, q), 40.3 (1C, t), 38.2 (1C, t), 36.2 (1C, s), 35.2 (1C, s), 30.2 (2C, q), 29.8 (2C, q), 19.7 (1C, q), 15.8 (1C, q). IR (KBr) 1244, 1271, 1682 cm⁻¹, MS (m/e) 274.2 (M+, 34.9), 259.1 (100.0), 260.2 (21.7), 189.1 (21.5).

EXAMPLE 11 Floral Aldehydic Perfume Composition

Classic floral aldehydic compositions were prepared by mixing the following ingredients:

    ______________________________________                                         Ingredients           Parts by Weight                                          ______________________________________                                         Oil Ylang             100                                                      Dimethyl-α-ionone                                                                              110                                                      Rose de Mai Absolute at 10%*                                                                         60                                                       Oil Patchouly Rectified                                                                              10                                                       Oil Sandalwood        10                                                       Oil Vetiver Reunion   10                                                       Hydroxy Citronellal   80                                                       Oil Clove             15                                                       Ethyl Vanillin at 10%*                                                                               30                                                       Vanillin at 10%*      20                                                       Coumarin              85                                                       Aldehyde C-10 at 10%* 40                                                       Aldehyde C-11 Undecylenic at 10%*                                                                    40                                                       Aldehyde C-12 Lauric at 10%*                                                                         40                                                       Oil Bois de Rose Brazilian                                                                           20                                                       Linalyl Acetate       10                                                       Essence Styrax        15                                                       Oakmoss Absolute at 50%*                                                                             20                                                       Mousse de Metra at 10%*                                                                              30                                                       α-Irone at 10%* 10                                                       Jasmin Absolute at 10%*                                                                              150                                                      Tincture Vanilla      40                                                       Aldehyde C-14 at 10%*  5                                                       Oil Rose Turkish at 10%*                                                                             15                                                       Linalool from Bois de Rose                                                                           35                                                       Total                 1000                                                      *In odorless diethyl phthalate.                                          

When 150 parts of the novel Compound 3a were added to 1000 parts of the above mixture, a floral aldehycic type composition having a richer, fuller, and more tenacious odor was obtained.

When 150 parts of a mixture of musk compounds, comprising 70 parts of Musk Ambrette, 50 parts of Musk Ketone, and 30 parts of Musk Xylene were added to 1000 parts of the above mixture, a floral aldehydic type composition having substantially similar organoleptic properties to the floral aldehydic type composition prepared with the novel Compound 3a resulted. The novel musk chemical 3a can therefore be used in nitro-musk formulations in place of known musk chemicals to achieve very similar organoleptic effects.

EXAMPLE 12 Perfume Composition of the Fougere Type

Fougere type compositions were prepared by mixing the following ingredients:

    ______________________________________                                         Ingredients          Parts by Weight                                           ______________________________________                                         Citronellol          10                                                        Dimethyl-α-ionone                                                                             10                                                        Geranyl Acetate      10                                                        Oil Labdanum Cistus at 10%*                                                                         10                                                        Oil Clove            10                                                        Labdanum Colorless at 10%*                                                                          30                                                        Benzyl Salicylate    20                                                        Oil Petitgrain Terpeneless                                                                          20                                                        Oil Orange Bitter    20                                                        Isoamyl Salicylate   30                                                        Coumarin             30                                                        Geraniol             30                                                        Oil Patchouly        30                                                        Oil Lavandin Grosso  50                                                        Oil Lavender Barreme at 38-42%                                                                      60                                                        Oakmoss Absolute at 50%*                                                                            100                                                       Oil Bergamot         250                                                       Total                720                                                       ______________________________________                                          *In odorless diethyl phthalate.                                          

When 120 parts of novel musk Compound 3a were added to 720 parts of the above mixture, a Fougere type composition having a warmer, animal, musky quality, with greater tenacity than the basic composition was obtained.

When 120 parts of a mixture of musk compounds comprising 60 parts of Musk Ambrette, 40 parts of Musk Ketone and 20 parts of Musk Xylene were added to 720 parts of the above mixture, a Fougere type composition having substantially similar organoleptic properties to that of the Fougere type composition prepared with the novel Compound 3a resulted. Novel musk chemical 3a can therefore be used in nitro-musk formulations in place of known musk chemicals to achieve very similar organoleptic effects.

EXAMPLE 13 Perfume Composition of the Oriental Bouquet Type

Oriental bouquet compositions were prepared by mixing the following ingredients:

    ______________________________________                                         Ingredients           Parts by Weight                                          ______________________________________                                         Aldehyde C-12 at 10%*  5                                                       Phenyl Ethyl Acetate   5                                                       Indole at 10%*         5                                                       Aldehyde C-11 Undecylenic at 10%*                                                                    10                                                       Oil Vetiver Haiti     10                                                       Amyl Cinnamic Aldehyde                                                                               15                                                       Oil Sandalwood E.I.   20                                                       Vanillin              20                                                       Tolu Balsam at 50%*   20                                                       Hexyl Cinnamic Aldehyde                                                                              25                                                       Oil Patchouly         30                                                       Benzoin Siam Resinoid at 50%*                                                                        40                                                       Oil Petitgrain Paraguay                                                                              50                                                       Heliotropin           50                                                       Citronellol           60                                                       Benzyl Acetate Extra  75                                                       Phenyl Ethyl Alcohol  200                                                      Oil Bergamot Reconstituted                                                                           210                                                      Total                 850                                                      ______________________________________                                          *In odorless diethyl phthalate.                                          

When 150 parts of the novel Compound 3c were added to 750 parts of the above mixture, an oriental bouquet type composition having a warm, sweet, voluminous musky character was obtained.

When 150 parts of a mixture of nitro-musk compounds, comprising 40 parts of Musk Xylene, 50 parts of Musk Ketone and 60 parts of Musk Ambrette were added to 750 parts of the above mixture, an oriental bouquet type composition having substantially similar organoleptic properties to the oriental bouquet type composition prepared with novel Compound 3c resulted. The novel musk Compound 3c can therefore be used in nitro-musk formulations in place of known musk chemicals to achieve very similar organoleptic effects.

EXAMPLE 14 Preparation of a Soap Compositions

A total of 300 g of soap chips, produced from unperfumed sodium base toilet soap, made of tallow and coconut oil, were mixed with 30 g of a 10% ethyl alcohol solution of Compound 3a or Compound 3c , until substantially homogenous compositions were obtained. The soap composition containing Compound 3a manifested an excellent musk aroma, sweet and exalting with the character of the macrocyclic musks. The soap compositon containing Compound 3c manifested a long-lasting, sweet, slightly woody, musky odor.

EXAMPLE 15 Preparation of a Solid Detergent Compositions

A total of 100 g of a high temperature detergent powder, as sold under the trademark "ORVUS", was mixed with 2 g of a 10% ethyl alcohol solution of Compound 3a or Compound 3c, until substantially homogenous compositions were obtained. The detergent composition containing Compound 3a manifested an excellent musk aroma, sweet and exalting, with the character of the macrocyclic musks. The detergent composition containing Compound 3c manifested a long-lasting, sweet, slightly woody, musky odor.

As will be apparent to those skilled in the art, in the light of the foregoing disclosure, many alterations, modifications, substitutions and combinations are possible in the practice of this invention without departing from the spirit or scope thereof. 

What is claimed is:
 1. The compounds having the structure: ##STR23## wherein R is hydrogen or methyl and, R₁ and R₂ are hydrogen, methyl, or ethyl.
 2. The compound having the structure: ##STR24##
 3. The compound having the structure: ##STR25##
 4. The compound having the structure: ##STR26##
 5. The compound having the structure: ##STR27##
 6. The compound having the structure: ##STR28##
 7. The compound having the structure: ##STR29##
 8. A fragrance composition comprising an organoleptically effective amount of a the compound(s) of claim 1 and at least one other organoleptic agent.
 9. A fragrance composition comprising an organoleptically effective amount of a compound of claim 2 and at least one other organoleptic agent.
 10. A fragrance composition comprising an organoleptically effective amount of a compound of claim 3 and at least one other organoleptic agent.
 11. A fragrance composition comprising an organoleptically effective amount of a compound of claim 4 and at least one other organoleptic agent.
 12. A fragrance composition comprising an organoleptically effective amount of a compound of claim 5 and at least one other organoleptic agent.
 13. A fragrance composition comprising an organoleptically effective amount of a compound of claim 6 and at least one other organoleptic agent.
 14. A method for modifying, enhancing or improving the organoleptic properties of perfume compositions, colognes and perfumed articles which comprises adding thereto an organoleptically effective amount of a compound of claim
 1. 